CN106318091B - A kind of aqueous dual-component organic-inorganic hybridization coating resin and preparation method thereof - Google Patents
A kind of aqueous dual-component organic-inorganic hybridization coating resin and preparation method thereof Download PDFInfo
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- CN106318091B CN106318091B CN201610695803.2A CN201610695803A CN106318091B CN 106318091 B CN106318091 B CN 106318091B CN 201610695803 A CN201610695803 A CN 201610695803A CN 106318091 B CN106318091 B CN 106318091B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
It is a kind of novel aqueous bi-component organic-inorganic hybridization coating resin and preparation method thereof the invention belongs to water paint field.Component A of the present invention is modified acrylic acid using polyester, alkyd, polyurethane, epoxy, organosilicon etc. based on acrylic acid, synthesizes the water-based acrylic resin dispersion with one or more of functional groups.Nano-oxide colloidal sol of the B component by sol-gal process synthesis with one or more of functional groups.While invention is by the inorganic modified performances such as ageing-resistant, water-fast, wear-resisting for improving common bicomponent material, it can obtain the wider range of organic/inorganic composite material of inorganic part ratio, and ensure the stability of organic/inorganic composite material in water, use water as diluent, reduction system VOC has the excellent feature of environmental protection.
Description
Technical field
The present invention relates to a kind of aqueous dual-component organic-inorganic hybridization coating resins and preparation method thereof, belong to aqueous
Paint field.
Background technique
In recent years, as the pressure of environment and resource increases, water paint is grown rapidly.Two component polyurethane Yin Qigao dress
Decorations property, high-weatherability, the advantages such as normal temperature self-drying occupy always very important position in paint field.And aqueous dual-component is poly-
The problem of urethane is due to expensive, easy to foaming, free isocyanate toxicity, using having limitation always.And amino resins
The amino-stoving varnish for making curing agent needs hot conditions, consumes resource and cost.And either aqueous polyurethane coating or aqueous ammonia
Base is coating material solidified, the requirement that resistance to ag(e)ing, corrosion resistance, wearability etc. all further increase.
Hybrid inorganic-organic materials become research and development focus at present, and organic component is introduced inorganic material on a molecular scale
In its toughness, film forming can be improved, conversely, inorganic component is introduced into organic material then can be improved its rigidity, color inhibition
Property, heat resistance and resistance to ag(e)ing.Organic-inorganic component carries out that molecular level is compound, the performance perfect combination both made together, energy
Realize the complementation of material property.Such as a kind of production method that water base silicon ion is acrylic resin modified of patent CN1616499A,
Under the action of silane coupling agent, modifying agent comprehensive silicon polymerize with acrylic acid-grafted, ambient cross-linking, improves resistance to ag(e)ing, water resistance
Deng.A kind of high-performance organic inorganic hybridization acrylate coatings material of patent CN1746236A and preparation method thereof, to contain hydroxyl
Base, alkoxy inorganic nanometer oxide colloidal sol be curing agent, react with the acrylate containing functional groups, crosslinking
It is solidified into hybrid inorganic-organic coating, improves hardness, thermal stability, scratch resistant, wearability and the ultraviolet shielded property of coating
Energy.But it is the serious problem of comparison that organic-inorganic material 50-1:1 is unstable, it is certainly dry which does not solve aqueous dual-component
The problem of coating.
Summary of the invention
The present invention is to belong to water paint field, provides a kind of aqueous dual-component organic-inorganic hybridized coatings use
Resin and preparation method thereof.This method passes through the inorganic modified property such as ageing-resistant, water-fast, wear-resisting for improving common bicomponent material
While energy, the wider range of organic/inorganic composite material of inorganic part ratio can be obtained, and ensure organic/inorganic composite material
Stability in aqueous reduces system VOC with water as diluent, has the excellent feature of environmental protection.
Component A of the present invention is based on acrylic acid, using polyester (alkyd), polyurethane, epoxy, organosilicon etc. to acrylic acid
It is modified, synthesizes the water-based acrylic resin dispersion with one or more of functional groups.B component passes through collosol and gel
Nano-oxide colloidal sol of the method synthesis with one or more of functional groups.A, the ratio of B component 50-1:1 after mixing,
Low-temperature bake or normal temperature self-drying film forming.Wherein the acrylic resin of component A contains carboxyl, hydroxyl, epoxy group, ketone carbonyl or amide
The nano-oxide colloidal sol of the functional groups such as base, B component contains hydroxyl, epoxy group, alkoxy, amino, isocyanate group, mercapto
The functional groups such as base.
Synthesize component A raw material group become modified resin 0-50 parts, 10-40 parts of acrylic monomers, function monomer 0.3-30
Part, 0-15 parts of reactive diluent, 3-50 parts of cosolvent, 0.1-10 parts of initiator, 1-10 parts of neutralizer, 1-20 parts of chain extender, water
0-70 parts.
Preferred synthesis component A raw material is modified resin 3-15 parts, 10-25 parts of acrylic monomers, 1-5 parts of function monomer,
0-5 parts of reactive diluent, 3-15 parts of cosolvent, 0.5-5 parts of initiator；0-5 parts of chain extender；40-65 parts of water.
Wherein modified resin is selected from polyester resin, alkyd resin, polyurethane resin, epoxy resin, organic siliconresin etc.
It is one or more of.
The monomeric polyol of the polyester resin of synthesis modification is selected from polycaprolactone polyol, polycarbonate polyol, gathers
The one or more such as tetrahydrofuran polyalcohol, neopentyl glycol, trimethylolpropane, 1,4 cyclohexane dimethanol, pentaerythrite；It is more
First acid monomers be selected from adipic acid, 1,4 cyclohexanedicarboxylic acid, M-phthalic acid, terephthalic acid (TPA), dimeric dibasic acid, trimellitic anhydride,
The one or more such as dihydromethyl propionic acid.
The monomeric polyol of the alkyd resin of synthesis modification is selected from polycaprolactone polyol, polycarbonate polyol, gathers
The one or more such as tetrahydrofuran polyalcohol, neopentyl glycol, trimethylolpropane, 1,4 cyclohexane dimethanol, pentaerythrite；Oil
Acid monomers are selected from the one or more such as dehydrated castor oleic acid, behenic acid, cocinic acid, eleostearic acid, linolenic acid, linoleic acid.
The isocyanate-monomer of synthesis modification polyurethane resin is selected from isoflurane chalcone diisocyanate, own diisocyanate
One or more of ester, hydrogenated toluene diisocyanate etc..
The epoxide equivalent of modified epoxy resin is 188-1000, is selected from E51, E44, E20, E12, one of or it is several
Kind.
The acrylic monomers of synthesis modification resin be selected from methyl methacrylate, methyl acrylate, ethyl methacrylate,
Butyl methacrylate, butyl acrylate, isobornyl methacrylate, Isooctyl acrylate monomer, methacrylic acid moon silicone grease, first
Base isobornyl acrylate, isobornyl acrylate, trifluoroethyl methacrylate, cyclohexyl methacrylate, acrylic acid ring
One or more of own ester.
Function monomer is selected from glycidyl methacrylate, N hydroxymethyl acrylamide, N- butoxy, methacryl
Amine, acrylamide, methacrylic acid, acrylic acid, methacrylic acid ring carbonic ether, hydroxyethyl methacrylate, acrylic acid hydroxyl second
Ester, hydroxy propyl methacrylate, hydroxypropyl acrylate, hydroxy butyl acrylate, vinyltrimethoxysilane, three second of vinyl
Oxysilane, vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane, diacetone acrylamide acyl
One or more of amine, methacrylic acid ethyl acetoacetate.
Reactive diluent is selected from one of tertiary carbonic acid glycidyl ester, trihydroxymethylpropanyltri diglycidyl ether etc. or several
Kind.
Cosolvent is selected from ethylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, isopropanol, isobutanol, just
One or more of butanol, propylene glycol monomethyl ether, butyl, ethyl alcohol, propylene glycol, diacetone alcohol, isooctanol.
Initiator be selected from azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, isopropyl benzene hydroperoxide,
One or more of two tertiary amyl peroxide, peroxidized t-butyl perbenzoate, peroxidating 2 ethyl hexanoic acid tert-butyl ester.
Neutralizer is selected from sodium hydroxide, ammonium hydroxide, triethylamine, triethanolamine, diethanol amine, N, N- dimethylethanolamine, second
One or more of acid, propionic acid, lactic acid.
The raw material group for synthesizing B component becomes presoma 3-50 parts, and 1-30 parts of water, 2-50 parts of solvent, catalyst and chelating
0.5-5 parts of agent, 0-15 parts of additive, 2-80 parts of coupling agent.
The raw material group of preferred synthesis B component becomes presoma 10-25 parts, and 1-5 parts of water, 5-15 parts of solvent, catalyst
And 0.5-3 parts of intercalating agent, 0-10 parts of additive, 50-70 parts of coupling agent.
Wherein precursor be selected from silicon, aluminium, zirconium, titanium alkoxide one or more, i.e. ethyl orthosilicate, four silicon of prestox ring
Oxygen alkane (D4), ten pregnancy basic rings, eight siloxanes (D8), aluminum oxide, titanium oxide, zirconium oxide, methyltriethoxysilane, two
The one or more such as methyldiethoxysilane.
Solvent is selected from methanol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol, propylene glycol, 1,4- butanediol, ethylene oxide, three ethyl alcohol
One or more of amine, dimethylbenzene, ethyl acetate etc..
Catalyst and chelating agent be selected from hydrochloric acid, p- toluenesulfonic acid, acetic acid, succinic acid, maleic acid, boric acid, sulfuric acid, nitric acid,
One or more of acetic acid, ammonium hydroxide, sodium hydroxide, EDTA and citric acid.
Additive is selected from acetylacetone,2,4-pentanedione, polyvinyl alcohol, ethanedioic acid oxalic acid, formamide, dimethylformamide, dioxane second
The one or more of alkane etc..
Coupling agent is selected from fluorosilicone, epoxy radical siloxane, amino silicone, vinylsiloxane, isocyanate group silicon
The one or more of oxygen alkane, sulfydryl siloxanes, functional acrylic monomer.Including gamma-aminopropyl-triethoxy-silane, vinyl three
Methoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, hydroxyethyl methacrylate, hydroxy-ethyl acrylate, methyl
Hydroxypropyl acrylate, hydroxypropyl acrylate, hydroxy butyl acrylate etc..
Component A concrete methods of realizing of the invention is as follows:
Bottom material hydrotropy is put into the reaction kettle equipped with agitating device, reflux condensate device, Dropping feeder and temperature regulating device
Agent, modified resin (or not adding), cosolvent, reactive diluent (or not adding), rise to 70- under certain mixing speed
160 DEG C, the mixed of acrylic monomers and function monomer and initiator in formula is added dropwise with the speed of 200r/min-500r/min substep
Close object, 3-5hr kept the temperature after completion of dropwise addition, less than 70 DEG C addition one or more neutralizers are cooled to after heat preservation, finally plus
Enter 40 DEG C of deionized water emulsification filtering and discharging.
B component concrete methods of realizing of the invention is as follows:
Investment is formulated step by step in the reaction kettle equipped with agitating device, reflux condensate device, Dropping feeder and temperature regulating device
Presoma, water, solvent, catalyst, the chelating agent (or not adding), additive, coupling agent of proportion, in 100r/min-500r/
40-100 DEG C of heat preservation is risen under min mixing speed, is cooled to after heat preservation close to room temperature, filtering and discharging.
Technical effect
Component A containing functional groups such as carboxyl, hydroxyl, epoxy group, ketone carbonyl or amide groups in the present invention with contain
The B component of the functional groups such as hydroxyl, epoxy group, alkoxy, amino, isocyanate group, sulfydryl is under room temperature or low-temperature bake
Cross-linking reaction forms the reticular structure of crosslinking.Two components are it can also happen that self-crosslinking reaction, forms fine and close film simultaneously.Separately
The problems such as common organo-mineral complexing modified resin is big because of easy gel viscosity, inorganic modified amount is limited, and the present invention at
This mechanism is utilized in membrane process, therefore substantially increases the degree of organo-mineral complexing, therefore performance greatly promotes.
The present invention has following advantage:
1, paint film thickness painting will not blister.The isocyanate group of aqueous double-component polyurethane resin and reacting for water are as follows:
HOH+2RNCO→RNHCOHNR+CO2↑
The CO2 that side reaction generates easily makes paint film generate the film defects such as prickly heat, bubble, and paint film is thicker, and phenomenon is more obvious.
Aqueous double-component polyurethane coating film thickness 50-60um in market has been not easy, and there is no generate gas or small point by the present invention
The by-product of son influences, and it is not blistering to can reach the painting of 120um thickness.
2, the surface tension of water-based system is reduced.Surface tension of the water at 20 DEG C is 72.7 dynes per centimeters, higher than solvent
Very much, the near 20-40 of system surface tension can just be made by needing to be added a large amount of auxiliary agents for reducing surface tension when water paint is applied
Dynes per centimeter, and while more low surface tension auxiliary agent reduces surface tension, also many negative effects are brought to film.
And the present invention without reduce surface tension auxiliary agent in the case where, water-based system surface tension can be down to 35-45 dynes/li
Rice, a small amount of auxiliary agent, which is only added, can make the surface tension of water-based system be down to 20-30 dynes per centimeter.
3, allow higher inorganic modified ratio, solve stability problem.General aqueous inorganic modified resin is due to steady
Qualitative and side reaction, inorganic modified ratio is generally less than 5%, and the present invention can make organic-inorganic ratio wide in range to 50-1:
1, i.e., inorganic modified ratio can reach 50%, and have good stability.
4, high glaze, high richness.The gloss of paint film (varnish) of the present invention can reach 90 or more 60 ° of angles, and DOI is greater than 90.
5, resistance to ag(e)ing, corrosion resistance, water resistance etc. are had excellent performance.Ageing-resistant experiment QUV-A is greater than 1500h.Paint of the present invention
Hydrophilic radical fundamental reaction of the film after fully crosslinked is complete therefore water-fast, corrosion resistance is excellent, low-temperature bake or directly does after doing solid work
Water-fast test room temperature is water-fast be greater than 10 days it is not blistering.
Embodiment
1 material proportion of embodiment such as following table
Component A implementation method, in the reaction kettle that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
The propylene glycol monobutyl ether of middle investment formula ratio, side stirring are added dropwise the about 3h of mix monomer 1 and drip off, keep the temperature 2h while being warming up to 115 DEG C
The about 0.5h of mix monomer 2 is added dropwise to drip off, adds peroxidized t-butyl perbenzoate, keeps the temperature 4h.N is added, N dimethyl ethanol amine divides
30min is dissipated, 40 DEG C of deionized waters, high speed dispersion 1h, filtering and discharging is added.
The preparation method of B component, in the reaction that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
Ethyl orthosilicate, dehydrated alcohol and the water that recipe ratio is put into kettle, are warming up to 55 DEG C of addition gamma-aminopropyl-triethoxy-silanes,
55 DEG C of heat preservation 5h, filtering and discharging.
2 material proportion of embodiment such as following table
The production method of component A, in the reaction that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
Propylene glycol methyl ether acetate, side stirring are put into kettle, while being warming up to 75 DEG C, the about 3h of mix monomer 1 are added dropwise and drips off, heat preservation 2h is added dropwise
The about 0.5hr of mix monomer 2 is dripped off, and adds azodiisobutyronitrile, keeps the temperature 4hr.70 DEG C of addition ethylenediamines, disperse 1hr, 60 degrees Celsius
Glacial acetic acid is added, disperses 30min, 40 DEG C of addition deionized waters, high speed dispersion 1hr, filtering and discharging.
The production method of B component, in the reaction that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
Methyltriethoxysilane, dehydrated alcohol, water, 1mol/L hydrochloric acid are put into kettle, are warming up to 55 DEG C of addition γ-glycidyl ether oxygens
Propyl trimethoxy silicane, 55 DEG C of heat preservation 5hr, filtering and discharging.
3 material proportion of embodiment such as following table
The preparation method of component A, in the reaction that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
E12 and ethylene glycol monobutyl ether, side stirring are put into kettle, while being warming up to 145 DEG C, the about 3hr of mix monomer 1 are added dropwise and drips off, keeps the temperature 2hr
The about 0.5hr of mix monomer 2 is added dropwise to drip off, adds di-tert-butyl peroxide, keeps the temperature 4hr.80 DEG C of addition N, N dimethyl ethyl alcohol
Amine disperses 1hr, 40 DEG C of addition deionized waters, high speed dispersion 1hr, filtering and discharging.
The preparation method of B component, in the reaction that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
The nitric acid that TiO2, ethyl orthosilicate, butanol, water, mass fraction 5% are put into kettle, is warming up to 55 DEG C of addition γ-glycidol ethers
Oxygen propyl trimethoxy silicane, 55 DEG C of heat preservation 5hr, filtering and discharging.
4 material proportion of embodiment such as following table
The preparation method of component A, in the reaction that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
Neopentyl glycol, dehydrated castor oleic acid, trimethylolpropane, adipic acid and dibutyl tin dilaurate are put into kettle, are slowly heated up
To 160 DEG C of insulation reaction 2hr, then slow temperature reaction is to 180 DEG C of insulation reaction 2hr, then ladder-elevating temperature, to 230 DEG C, heat preservation is anti-
150 DEG C should be cooled to acid value < 10mgKOH/g, propylene glycol monobutyl ether is added, mix monomer 1 is added dropwise about after being warming up to 155 DEG C
3hr is dripped off, and heat preservation 2hr is added dropwise the about 0.5hr of mix monomer 2 and drips off, and adds isopropyl benzene hydroperoxide, keeps the temperature 4hr.It is cooled to 80 DEG C
Diethylenetriamine is added, stirs 30min, 40 DEG C of addition deionized waters, high speed dispersion 1hr, filtering and discharging.
The preparation method of B component, in the reaction that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
Ethyl orthosilicate, dehydrated alcohol, water are put into kettle, are warming up to 80 DEG C of addition γ-glycidyl ether oxygen propyl trimethoxy silicanes,
Ammonium hydroxide, 80 DEG C of heat preservation 5h, filtering and discharging is added.
5 material proportion of embodiment such as following table
The preparation method of component A, in the reaction that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
Polycarbonate glycol, dibutyl tin dilaurate are put into kettle, is warming up to 80 DEG C, and monomer hexamethylene diisocyanate, heat preservation is added dropwise
React 2hr.Adipic acid, neopentyl glycol, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, then slow temperature reaction is added to 180 DEG C of insulation reactions
2hr, then ladder-elevating temperature, to 230 DEG C, insulation reaction to acid value < 10mgKOH/g is cooled to 150 DEG C, and ethylene glycol monobutyl ether is added,
The about 3hr of mix monomer 1 is added dropwise after being warming up to 155 DEG C to drip off, heat preservation 2hr is added dropwise the about 0.5hr of mix monomer 2 and drips off, and adds isopropyl
Benzene hydrogen peroxide keeps the temperature 4hr.80 DEG C of addition triethylene tetramines are cooled to, 30min is stirred, 60 DEG C of addition lactic acid stir 15min,
40 DEG C of addition deionized waters, high speed dispersion 1hr, filtering and discharging.
The preparation method of B component, in the reaction that agitating device, reflux condensate device, Dropping feeder and temperature regulating device are housed
γ-glycidyl ether oxygen propyl trimethoxy silicane, dehydrated alcohol, water are put into kettle, are warming up to 80 DEG C of addition ammonium hydroxide, 80 DEG C of guarantors
Warm 5h, filtering and discharging.
Claims (13)
1. a kind of aqueous dual-component organic-inorganic hybridization coating resin, is made of A, B component:
Synthesize component A raw material be modified resin 3-15 parts, 10-25 parts of acrylic monomers, 1-5 parts of function monomer, reactive diluent
0-5 parts, 3-15 parts of cosolvent, 0.5-5 parts of initiator, 0-5 parts of chain extender, 40-65 parts of water；
Component A utilizes polyester resin, alkyd resin, polyurethane resin, epoxy resin or silicone resin based on acrylic acid
Acrylic acid is modified, the water-based acrylic resin dispersion with one or more of functional groups is synthesized；
The raw material group for synthesizing B component becomes presoma 10-25 parts, and 1-5 parts of water, 5-15 parts of solvent, catalyst and intercalating agent
0.5-3 parts, 0-10 parts of additive, 50-70 parts of coupling agent；
Synthesize B component presoma be selected from silicon, aluminium, zirconium, titanium alkoxide one or more.
2. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that:
The monomeric polyol of the polyester resin of synthesis modification is selected from polycaprolactone polyol, polycarbonate polyol, poly- tetrahydro
Furan polyols, neopentyl glycol, trimethylolpropane, 1,4 cyclohexane dimethanol, pentaerythrite are one or more of；
The polyacid monomer of the polyester resin of synthesis modification is selected from adipic acid, 1,4 cyclohexanedicarboxylic acid, M-phthalic acid, right
Phthalic acid, dimeric dibasic acid, trimellitic anhydride, dihydromethyl propionic acid are one or more of.
3. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that:
The monomeric polyol for synthesizing the modified alkyd resin of component A is selected from polycaprolactone polyol, polycarbonate polyol, gathers
Tetrahydrofuran polyalcohol, neopentyl glycol, trimethylolpropane, 1,4 cyclohexane dimethanol, pentaerythrite are one or more of；
Synthesize the modified alkyd resin oleic acid monomer of component A selected from dehydrated castor oleic acid, behenic acid, cocinic acid, eleostearic acid,
Linolenic acid, linoleic acid are one or more of.
4. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that: synthesis A
The isocyanate-monomer of modified polyurethane resin is selected from isoflurane chalcone diisocyanate, hexamethylene diisocyanate, hydrogenation in component
One or more of toluene di-isocyanate(TDI).
5. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that: synthesis A
The epoxide equivalent of component modification epoxy resin is 188-1000, selected from one or more of E51, E44, E20, E12.
6. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that: synthesis A
The acrylic monomers of component be selected from methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl methacrylate,
Butyl acrylate, isobornyl methacrylate, Isooctyl acrylate monomer, lauryl methacrylate, methacrylic acid isoborneol
One of ester, isobornyl acrylate, trifluoroethyl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate or
It is several.
7. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that: synthesis A
Component function monomer is selected from glycidyl methacrylate, N hydroxymethyl acrylamide, N- butoxy methyl acrylamide, third
Acrylamide, methacrylic acid, acrylic acid, methacrylic acid cyclic carbonate ester, hydroxyethyl methacrylate, hydroxy-ethyl acrylate, first
Base hydroxypropyl acrylate, hydroxypropyl acrylate, hydroxy butyl acrylate, vinyltrimethoxysilane, vinyl triethoxyl
Silane, vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane, Diacetone Acrylamide, first
One or more of base acrylic acid ethyl acetoacetate.
8. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that: synthesis A
Component cosolvent is selected from ethylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, isopropanol, isobutanol, positive fourth
One or more of alcohol, propylene glycol monomethyl ether, butyl, ethyl alcohol, propylene glycol, diacetone alcohol, isooctanol.
9. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that: synthesis A
Component initiator is selected from azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, isopropyl benzene hydroperoxide, two spies
One or more of amyl peroxide, peroxidized t-butyl perbenzoate, peroxidating 2 ethyl hexanoic acid tert-butyl ester.
10. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that: synthesis
B component solvent be selected from methanol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol, propylene glycol, 1,4- butanediol, ethylene oxide, triethanolamine,
One or more of dimethylbenzene, ethyl acetate.
11. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that: synthesis
B component catalyst and chelating agent are selected from hydrochloric acid, p- toluenesulfonic acid, acetic acid, succinic acid, maleic acid, boric acid, sulfuric acid, nitric acid, ammonia
One or more of water, sodium hydroxide, EDTA and citric acid.
12. a kind of aqueous dual-component organic-inorganic hybridization coating resin as described in claim 1, it is characterised in that: synthesis
B component coupling agent is selected from fluorosilicone, epoxy radical siloxane, amino silicone, vinylsiloxane, isocyanate group silicon oxygen
The one or more of alkane, sulfydryl siloxanes.
13. a kind of aqueous dual-component organic-inorganic hybridization coating resin as claimed in claim 12, it is characterised in that: close
Gamma-aminopropyl-triethoxy-silane, vinyltrimethoxysilane, γ-glycidyl ether oxygen propyl are selected from B component coupling agent
One or more of trimethoxy silane.
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| CN1831070A (en) * | 2006-03-06 | 2006-09-13 | 复旦大学 | Excellent corrosion-proof performance organic-inorganic hybridized coatings and its prepn. method |
| KR100845403B1 (en) * | 2007-04-16 | 2008-07-10 | 유창국 | Manufacturing method for organic-inorganic hybrid coating solution for ambient thermal polymerization |
| CN102675518B (en) * | 2012-06-01 | 2014-08-06 | 江南大学 | Preparation method for organic-inorganic hybrid fluorine-silicon modified nano waterborne resin |
| CN103554381A (en) * | 2013-10-21 | 2014-02-05 | 北京金汇利应用化工制品有限公司 | Water-based acrylic acid modified saturated polyester resin and preparation method thereof |
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